Reversible addition-fragmentation chain transfer polymerization of vinyl chloride

Carlos M.R. Abreu; Patrícia V. Mendonça; Arménio C. Serra; Jorge F.J. Coelho; Anatoliy V. Popov; Ganna Gryn'ova; Michelle L. Coote; Tamaz Guliashvili

doi:10.1021/ma300064j

Reversible addition-fragmentation chain transfer polymerization of vinyl chloride

Carlos M.R. Abreu, Patrícia V. Mendonça, Arménio C. Serra, Jorge F.J. Coelho^*, Anatoliy V. Popov, Ganna Gryn'ova, Michelle L. Coote, Tamaz Guliashvili

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

66 Citations (Scopus)

Abstract

Controlled/"living" radical polymerization (CLRP) of vinyl chloride (VC) via the reversible addition-fragmentation chain transfer (RAFT) process is reported for the first time. The cyanomethyl methyl(phenyl) carbamodithioate (CMPCD) was found to be an efficient RAFT agent enabling the CLRP polymerization of VC monomer under certain experimental conditions. Two different radical initiators, having very distinct half-life times at room temperature, were employed in this study. The kinetic studies of RAFT polymerization of VC show a linear increase of the molecular weight with the monomer conversion and the lowest polydispersity (PDI) ever reported for poly(vinyl chloride) (PVC) synthesized with CLRP method (PDI ∼ 1.4). The resulting PVC was fully characterized using the matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS), ¹H nuclear magnetic resonance spectroscopy ( ¹H NMR), and gel permeation chromatography (GPC) techniques. The ¹H NMR and MALDI-TOF-MS analysis of PVC prepared via RAFT polymerization method have shown the absence of structural defects and the presence of chain-end functional groups. The "livingness" of the PVC was also confirmed by a successful reinitiation experiment. The suitability of the RAFT agent was also confirmed via high-level ab initio molecular orbital calculations.

Original language	English
Pages (from-to)	2200-2208
Number of pages	9
Journal	Macromolecules
Volume	45
Issue number	5
DOIs	https://doi.org/10.1021/ma300064j
Publication status	Published - 13 Mar 2012

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@article{04405fff2dfd43efa4811c06a8aff5c8,

title = "Reversible addition-fragmentation chain transfer polymerization of vinyl chloride",

abstract = "Controlled/{"}living{"} radical polymerization (CLRP) of vinyl chloride (VC) via the reversible addition-fragmentation chain transfer (RAFT) process is reported for the first time. The cyanomethyl methyl(phenyl) carbamodithioate (CMPCD) was found to be an efficient RAFT agent enabling the CLRP polymerization of VC monomer under certain experimental conditions. Two different radical initiators, having very distinct half-life times at room temperature, were employed in this study. The kinetic studies of RAFT polymerization of VC show a linear increase of the molecular weight with the monomer conversion and the lowest polydispersity (PDI) ever reported for poly(vinyl chloride) (PVC) synthesized with CLRP method (PDI ∼ 1.4). The resulting PVC was fully characterized using the matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS), 1H nuclear magnetic resonance spectroscopy ( 1H NMR), and gel permeation chromatography (GPC) techniques. The 1H NMR and MALDI-TOF-MS analysis of PVC prepared via RAFT polymerization method have shown the absence of structural defects and the presence of chain-end functional groups. The {"}livingness{"} of the PVC was also confirmed by a successful reinitiation experiment. The suitability of the RAFT agent was also confirmed via high-level ab initio molecular orbital calculations.",

author = "Abreu, {Carlos M.R.} and Mendon{\c c}a, {Patr{\'i}cia V.} and Serra, {Arm{\'e}nio C.} and Coelho, {Jorge F.J.} and Popov, {Anatoliy V.} and Ganna Gryn'ova and Coote, {Michelle L.} and Tamaz Guliashvili",

year = "2012",

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doi = "10.1021/ma300064j",

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T1 - Reversible addition-fragmentation chain transfer polymerization of vinyl chloride

AU - Abreu, Carlos M.R.

AU - Mendonça, Patrícia V.

AU - Serra, Arménio C.

AU - Coelho, Jorge F.J.

AU - Popov, Anatoliy V.

AU - Gryn'ova, Ganna

AU - Coote, Michelle L.

AU - Guliashvili, Tamaz

PY - 2012/3/13

Y1 - 2012/3/13

N2 - Controlled/"living" radical polymerization (CLRP) of vinyl chloride (VC) via the reversible addition-fragmentation chain transfer (RAFT) process is reported for the first time. The cyanomethyl methyl(phenyl) carbamodithioate (CMPCD) was found to be an efficient RAFT agent enabling the CLRP polymerization of VC monomer under certain experimental conditions. Two different radical initiators, having very distinct half-life times at room temperature, were employed in this study. The kinetic studies of RAFT polymerization of VC show a linear increase of the molecular weight with the monomer conversion and the lowest polydispersity (PDI) ever reported for poly(vinyl chloride) (PVC) synthesized with CLRP method (PDI ∼ 1.4). The resulting PVC was fully characterized using the matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS), 1H nuclear magnetic resonance spectroscopy ( 1H NMR), and gel permeation chromatography (GPC) techniques. The 1H NMR and MALDI-TOF-MS analysis of PVC prepared via RAFT polymerization method have shown the absence of structural defects and the presence of chain-end functional groups. The "livingness" of the PVC was also confirmed by a successful reinitiation experiment. The suitability of the RAFT agent was also confirmed via high-level ab initio molecular orbital calculations.

AB - Controlled/"living" radical polymerization (CLRP) of vinyl chloride (VC) via the reversible addition-fragmentation chain transfer (RAFT) process is reported for the first time. The cyanomethyl methyl(phenyl) carbamodithioate (CMPCD) was found to be an efficient RAFT agent enabling the CLRP polymerization of VC monomer under certain experimental conditions. Two different radical initiators, having very distinct half-life times at room temperature, were employed in this study. The kinetic studies of RAFT polymerization of VC show a linear increase of the molecular weight with the monomer conversion and the lowest polydispersity (PDI) ever reported for poly(vinyl chloride) (PVC) synthesized with CLRP method (PDI ∼ 1.4). The resulting PVC was fully characterized using the matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS), 1H nuclear magnetic resonance spectroscopy ( 1H NMR), and gel permeation chromatography (GPC) techniques. The 1H NMR and MALDI-TOF-MS analysis of PVC prepared via RAFT polymerization method have shown the absence of structural defects and the presence of chain-end functional groups. The "livingness" of the PVC was also confirmed by a successful reinitiation experiment. The suitability of the RAFT agent was also confirmed via high-level ab initio molecular orbital calculations.

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U2 - 10.1021/ma300064j

DO - 10.1021/ma300064j

M3 - Article

SN - 0024-9297

VL - 45

SP - 2200

EP - 2208

JO - Macromolecules

JF - Macromolecules

IS - 5

ER -

Reversible addition-fragmentation chain transfer polymerization of vinyl chloride

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